CH<sub>2</sub> Scissor and Twist Vibrations of Liquid Polyethylene Glycol——Raman Spectra and Density Functional Theory Calculations

doi:10.3866/PKU.WHXB201702083

Acta Phys. -Chim. Sin.

2017, Vol. 33

Issue (5): 1043-1050 DOI: 10.3866/PKU.WHXB201702083

ARTICLE

CH₂ Scissor and Twist Vibrations of Liquid Polyethylene Glycol——Raman Spectra and Density Functional Theory Calculations

Lei HAN¹,Li PENG¹,Ling-Yun CAI¹,Xu-Ming ZHENG¹,Fu-Shan ZHANG^2,*(

)

¹ Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China
² Technology Center, Hengan Group, Jinjiang 362261, Fujian Province, P. R. China

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Abstract

A new method is developed to effectively study the contributions of various coexisting conformations to the actual vibrational spectrum of liquid polyethylene oxide (PEO). By defining six conformations for the-(CH₂CH₂O)-unit, four isomers from the combinations of all the same EO conformations [(TGT)₁₀, (TTT)₁₀, (TTG)₁₀, and (GTG)₁₀] and three isomers from the combinations of other EO conformations were constructed. Their optimized geometric structures and the corresponding vibrational frequencies were then computed. The unified standards that describe the different types of the CH₂ scissor and CH₂ twist vibrational modes for PEO400 are proposed through the analysis of the normal modes. The relationships between the four CH₂CH₂-OCH₂CH₂ conformations and the various CH₂ scissor and CH₂ twist vibrational modes and frequencies are determined, and the results are used to assign the practical vibrational spectra.

Key words： Polyethylene oxide Conformation Raman spectrum Density functional theory calculation

Received: 28 November 2016 Published: 08 February 2017

O641

Fund: the National Natural Science Foundation of China(21473163);National Basic Research Program of China (973)(2013CB834604)

Corresponding Authors: Fu-Shan ZHANG E-mail: zxm@zstu.edu.cn

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Lei HAN,Li PENG,Ling-Yun CAI,Xu-Ming ZHENG,Fu-Shan ZHANG. CH₂ Scissor and Twist Vibrations of Liquid Polyethylene Glycol——Raman Spectra and Density Functional Theory Calculations. Acta Phys. -Chim. Sin., 2017, 33(5): 1043-1050.

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http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201702083 OR http://www.whxb.pku.edu.cn/Y2017/V33/I5/1043

Fig 1 Six conformations of the-[CH₂CH₂O]-unit

Table 1 Seven geometric conformations of PEO400 and the corresponding dihedral angles computed using B3LYP/6-31G (d) level of theory

Fig 2 Seven conformational structures of PEO400 obtained using the PCM solvent model atB3LYP/6-31G (d) level of theory

Fig 3 FT-IR (top) and Raman (middle) spectra of neatliquid PEO400, and Raman spectrum (bottom) ofn(PEO400) : n(H₂O) = 1 : 1 sample Raman excitation wavelength = 488 nm

Fig 4 (a) Comparison between the experimental Raman spectrum of sample and the calculated TGT Raman spectrum using B3LYP/6-31G (d) level of theory and (b) linear regression fitting between main experimental Raman frequencies andthe corresponding calculated ones Raman excitation wavelength = 488 nm

Table 2 Calculated vibrational frequencies of (TGT)₁₀ conformation using PCM solvent model andB3LYP/6-31G (d) level of theory, the experimental frequencies and the assignments of PEO400

Fig 5 Calculated Raman spectra of seven PEO400 conformations in 1300-1600 cm^-1 region

Fig 6 Four CH₂CH₂-O-CH₂CH₂ conformations associated with the description of CH₂ scissor and CH₂ twist vibrations

1	Miyazawa T. ; Fukushima K. ; Ideguchi Y. J. Chem. Phys 1962, 37, 2764.
2	Yoshihara T. ; Tadokoro H. ; Murahashi S. J. Chem. Phys 1964, 41, 2902.
3	Koenig J. L. ; Angood A. C. J. Polym. Sci. A 1970, 8, 1787.
4	Tadokoro H. ; Chatani Y. ; Yoshihara T. ; Tarahara S. ; Murahashi S. Makromol. Chem 1964, 73, 109.
5	Matsuura H. ; Miyazawa T. J. Polym. Sci. A 1969, 7, 1735.
6	Takahashi Y. ; Tadokoro H. Macromolecules 1973, 6, 673.
7	Matsuura H. ; Miyazawa T. Bull. Chem. Soc. Jap 1968, 41, 1798.
8	Yakoyama M. ; Ochi H. ; Tadokoro H. ; Price C. Macromolecules 1972, 5, 690.
9	Rabolt J. F. ; Johnson K.W. ; Zitter R. N. J. Chem. Phys 1974, 61, 504.
10	Migliardo F. ; Magazù S. ; Caccamo M. T. J. Mol. Struct 2013, 1048, 261.
11	Chaurasia S. K. ; Singh R. K. ; Chandra S. Vibrational Spectroscopy 2013, 68, 190.
12	Frech R. ; Huang W. Macromolecules 1995, 28, 1246.
13	Chatani Y. ; Fujii Y. ; Takayanagi T. ; Homma A. Polymer 1990, 31, 2238.
14	Chatani Y. ; Okamura S. Polymer 1987, 28, 1815.
15	Iwamoto R. ; Saito Y. ; Ishihara H. ; Tadokoro H. J. Polym. Sci. Polym. Phys. Ed. 1968, 6, 1509.
16	Yokoyama M. ; Ishihara H. ; Iwamoto R. ; Tadokoro H. Macromolecules 1969, 2, 184.
17	Paoke B. L. ; Ratner M. A. ; Shriver D. F. J. Phys. Chem. Solids 1981, 42, 493.
18	Shephard J. J. ; Bremer P. J. ; McQuillan A. J. J. Phys. Chem. B 2009, 113, 14229.

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